Novel photosensitive resin compositions

ABSTRACT

A positive-working photosensitive composition comprising one or more polybenzoxazole precursor polymers, a diazonaphthoquinone photoactive compound which is the condensation product of a compound containing from 2 to about 9 aromatic hydroxyl groups with a 5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinone diazide sulfonyl compound, and at least one solvent, and the use of such compositions to form a relief pattern on a substrate thereby forming a coated substrate.

RELATED APPLICATIONS

This application claims priority from U.S. Provisional PatentApplication No. 60/511,198 filed Oct. 15, 2003.

FIELD OF THE INVENTION

The present invention relates to positive photosensitive resincompositions. More specifically, the present invention relates to apositive-working, aqueous base developable photosensitivepolybenzoxazole (PBO) precursor compositions, a process of use for saidphotosensitive composition, and electronic parts produced by saidprocess of use.

BACKGROUND OF THE INVENTION

In microelectronic applications, polymers that demonstrate hightemperature resistance are generally well known. Precursors of suchpolymers, such as polyimides and polybenzoxazoles can be madephotoreactive with suitable additives. The precursors are converted tothe desired polymer by known techniques such as exposure to hightemperatures. The polymer precursors are used to prepare protectivelayers, insulating layers, and relief structures of highlyheat-resistant polymers.

Conventional positive-working photosensitive polybenzoxazoles (PBO)contain an alkaline soluble PBO precursor and a diazoquinone photoactivecompound as shown in U.S. Pat. No. 4,371,685. The diazoquinone compoundinhibits the solubility of the PBO precursor in an aqueous base. Afterexposure to light, the diazoquinone compound undergoes photolysis andconverts to indenecarboxylic acid, which promotes the aqueous basesolubility of the PBO precursor. U.S. Pat. Nos. 6,177,225 and 6,127,086teach the use of a PBO precursor, which contains diazoquinone moietiesattached to its backbone along with a diazoquinone photoactive compoundin positive-working photosensitive polybenzoxazole (PBO) compositions.Recently U.S. patent application Ser. No. 10/793337 disclosed acomposition containing a polybenzoxazole precursor backbone mixed with aPBO precursor, which contained diazoquinone moieties attached to itsbackbone and at least one photoactive compound such as a diazoquinonecompound. U.S. patent application Ser. No. 10/796587 disclosed acomposition based on a PBO precursor, which contained diazoquinonemoieties attached to its backbone and had the amines at the end of thepolymer chain capped by various moieties and a diazoquionone photoactivecompound. U.S. patent application Ser. No. 10/793341 disclosesphotosensitive polybenzoxazole precursor compositions that containeddiazoquinone moieties attached to its backbone and containeddiazoquinone compounds without active hydrogen in their structures. Suchcompositions provided light color films upon curing. U.S. patentapplication Ser. No. 10/796587 also disclosed a composition containing aPBO precursor, which contained diazoquinone moieties attached to itsbackbone and had the amines at the end of polymer chain capped byvarious moieties and had at least one photoactive compound (PAC) withoutactive hydrogen to produce a light color film upon curing. In the artdescribed above, the diazoquinone moiety employed in the photoactivecompound was of a single type. Mixed diazoquinone compounds were notconsidered.

U.S. Pat. No. 4,818,658 disclosed a photoactive compound that was thereaction product of curcumin with 5-naphthoquinone diazide sulfonylcompounds and 4-naphthoquinone diazide sulfonyl compounds. U.S. Pat. No.5,612,164 disclosed a positive photoresist comprising atrihydroxyphenylethane containing both 5-naphthoquinone diazide sulfonylgroup and 4-naphthoquinone diazide sulfonyl group, and atrihydroxybenzophenone containing both 5-naphthoquinone diazide sulfonylgroup and 4-naphthoquinone diazide sulfonyl group. German Patent No. DD289,265 disclosed a photoactive compound containing both5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazidesulfonyl group. U.S. Pat. No. 6,524,764 disclosed positive-typephotosensitive polyimide and polybenzoxazole precursor compositions withphotoactive compound containing both 5-naphthoquinone diazide sulfonylgroup and 4-naphthoquinone diazide sulfonyl group. The 5-naphthoquinonediazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group couldbe in the same molecule or in a mixture of two photoactive components.

SUMMARY OF THE INVENTION

The applicants surprisingly discovered that PBO compositions comprisinga polybenzoxaxole precursor resin and photoactive compounds containingboth 5-naphthoquinone diazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group have superior lithographic performance to thosecompositions comprising a polybenzoxaxole precursor resin andphotoactive compounds containing only 5-naphthoquinone diazide sulfonylor only 4-naphthoquinone diazide sulfonyl.

Photosensitive formulations based on photoactive compounds containingboth 5-naphthoquinone diazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group have good imaging and mechanical properties aswell as superior shelf life stability.

The present invention discloses a positive photosensitive resincomposition comprising:

-   -   (a) one or more polybenzoxazole precursor polymers having        structure (II) or structure (IV);        wherein Ar¹ is a tetravalent aromatic group, a tetravalent        heterocyclic group, or mixtures thereof; Ar² is a divalent        aromatic, a divalent heterocyclic, a divalent alicyclic, or a        divalent aliphatic group that may contain silicon; Ar³ is a        divalent aromatic group, a divalent aliphatic group, a divalent        heterocyclic group, or mixtures thereof; Ar⁴ is Ar¹(OD)_(k)        ¹(OH)_(k) ² or Ar², x is from about 10 to about 1000; y is from        0 to about 900; D is one of the following moieties:        wherein R is H, halogen, C₁-C₄ alkyl group, C₁-C₄ alkoxy group,        cyclopentyl or cyclohexyl; k¹ can be any positive value of up to        about 0.5, k² can be any value from about 1.5 to about 2 with        the proviso that (k¹+k²)=2, G is a monovalent organic group        having a carbonyl, carbonyloxy or sulfonyl group,    -   (b) a diazonaphthoquinone photoactive compound which is the        condensation product of a compound containing from 2 to about 9        aromatic hydroxyl groups with a 5-naphthoquinone diazide        sulfonyl compound and a 4-naphthoquinone diazide sulfonyl        compound, and    -   (c) at least one solvent.

The present invention also concerns a process for forming a reliefpattern and electronic parts using the photosensitive composition. Theprocess comprises the steps of:

-   -   (a) coating on a suitable substrate, a positive-working        photosensitive composition comprising one or more        polybenzoxazole precursor polymers having any of the        structures (II) or (IV), a photosensitive agent which is the        condensation product of reaction of compound containing from 2        to about 9 aromatic hydroxyl groups with a 5-naphthoquinone        diazide sulfonyl compound and a 4-naphthoquinone diazide        sulfonyl compound, and at least one solvent, thereby forming a        coated substrate;    -   (b) prebaking the coated substrate;    -   (c) exposing the prebaked coated substrate to actinic radiation;    -   (d) developing the exposed coated substrate with an aqueous        developer, thereby forming an uncured relief image on the coated        substrate; and    -   (e) baking the developed coated substrate at an elevated        temperature, thereby curing the relief image.

DETAILED DESCRIPTION OF THE INVENTION

The first embodiment of the present invention discloses a positivephotosensitive resin composition comprising:

-   -   (a) one or more polybenzoxazole precursor polymers having        structure (II) or structure (IV)        wherein Ar¹ is a tetravalent aromatic group, a tetravalent        heterocyclic group, or mixtures thereof; Ar² is a divalent        aromatic, a divalent heterocyclic, a divalent alicyclic, or a        divalent aliphatic group that may contain silicon; Ar³ is a        divalent aromatic group, a divalent aliphatic group, a divalent        heterocyclic group, or mixtures thereof; Ar⁴ is Ar¹(OD)_(k)        ¹(OH)_(k) ² or Ar², x is from about 10 to about 1000; y is from        0 to about 900; D is one of the following moieties:        wherein, R is H, halogen, C₁-C₄ alkyl group, C₁-C₄ alkoxy group,        cyclopentyl, or cyclohexyl;        k¹ can be any positive value of up to about 0.5, k² can be any        value from about 1.5 to about 2 with the proviso that (k¹+k²)=2,        G is a monovalent organic group having a carbonyl, carbonyloxy        or sulfonyl group;    -   (b) at least one photoactive compound which is the condensation        product of a compound containing from 2 to about 9 aromatic        hydroxyl groups with a 5-naphthoquinone diazide sulfonyl        compound and a 4-naphthoquinone diazide sulfonyl compound, and    -   (c) at least one solvent.

Polymers of Structures (II)) can be prepared from polymers of Structure(I) in one step.

Polymer of Structure (I) can be prepared from monomers having Structures(V), (VI), (VII). Monomers having Structures (V), (VI), (VII) arereacted in the presence of a base to synthesize polybenzoxazoleprecursor polymers of Structure (I).

In Structures (I), (V), (VI) and (VII) Ar¹, Ar², Ar³, x, and y are aspreviously defined, and W is C(O)Cl, COOH or C(O)OR² and wherein R² isC₁-C₇ linear or branched alkyl group or a C₅-C₈ cycloalkyl group.

In Structures (II), (IV) and (V), Ar¹ is a tetravalent aromatic or atetravalent heterocyclic group. Examples of Ar¹ include but are notlimited to:

wherein X¹ is —O—, —S—, —C(CF₃)₂—, —C(CH₃)₂—, —CH₂—, —SO₂—, —NHCO— or—SiR¹ ₂— and each R¹ is independently a C₁-C₇ linear or branched alkylor C₅-C₈ cycloalkyl group. Examples of R¹ include, but are not limitedto, —CH₃, —C₂H₅, n-C₃H₇, i-C₃H₇, n-C₄H₉, t-C₄H₉, and cyclohexyl.

Examples of monomers having the Structure (V) containing Ar¹ include butare not limited to 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,3,3′-dihydroxy-4,4′-diaminodiphenylether, 3,3′-dihydroxybenzidine,4,6-diaminoresorcinol, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. Thesubstitution pattern of the two hydroxy and two amino groups in themonomer of Structure (V) may be any of the possible substitutionpatterns with the proviso that the each amino group has an orthorelationship with a hydroxyl group in order to be able to form thebenzoxaxole ring. Furthermore, the polybenzoxazole precursor basepolymer, may be synthesized using a mixture of two or more monomersdescribed by generic Structure V.

In Structures (II), (IV) and (VI), Ar² is a divalent aromatic, adivalent heterocyclic, a divalent alicyclic, or a divalent aliphaticgroup that may contain silicon. Examples of Ar² include but are notlimited to:

wherein X¹ is as defined before, X² is —O—, —S—, —C(CF₃)₂—, —C(CH₃)₂—,—CH₂—, —SO₂—, or —NHCO—, Z=H or C₁-C₈ linear, branched or cyclic alkyland p is an integer from 1 to 6. Examples of suitable Z groups include,but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl and cyclooctyl.

Examples of monomers having the Structure (VI) containing Ar² include,but are not limited to,5(6)-diamino-1-(4-aminophenyl)-1,3,3-trimethylindane (DAPI),m-phenylenediamine, p-phenylenediamine,2,2′-bis(trifluoromethyl)-4,4′-diamino-1,1′-biphenyl,3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether,2,4-tolylenediamine, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenylmethane,3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ketone,3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 1,3-bis(4-aminophenoxy) benzene, 1,3-bis(3-aminophenoxy) benzene, 1,4-bis(γ-aminopropyl)tetramethyldisiloxane,2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine,p-xylylenediamine, methylenediamine, tetramethylenediamine,pentamethylenediamine, hexamethylenediamine,2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine,heptamethylenediamine, 2,5-dimethylheptamethylenediamine,3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,octamethylenediamine, nonamethylenediamine,2,5-dimethylnonamethylenediamine, decamethylenediamine, ethylenediamine,propylenediamine, 2,2-dimethylpropylenediamine,1,10-diamino-1,10-dimethyldecane, 2,11-diaminidodecane,1,12-diaminooctadecane, 2,17-diaminoeicosane,3,3′-dimethyl-4,4′-diaminodiphenylmethane,bis(4-aminocyclohexyl)methane, 3,3′-diaminodiphenylethane,4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide,2,6-diaminopyridine, 2,5-diaminopyridine,2,6-diamino-4-trifluoromethylpyridine, 2,5-diamino-1,3,4,-oxadiazole,1,4-diaminocyclohexane, 4,4′-methylenedianiline,4,4′-methylene-bis(o-choloroaniline),4,4′-methylene-bis(3-methylaniline), 4,4′-methylene-bis(2-ethylaniline),4,4′-methylene-bis(2-methoxyaniline), 4,4′-oxy-dianiline,4,4′-oxy-bis-(2-methoxyaniline), 4,4′-oxy-bis-(2-chloroaniline),4,4′-thio-dianiline, 4,4′-thio-bis-(2-methylaniline),4,4′-thio-bis-(2-methyoxyaniline), 4,4′-thio-bis-(2-chloroaniline).Futhermore, the polybenzoxazole precursor base polymer, may besynthesized using a mixture of two or more monomers described by genericStructure VI.

In Structures (II), (IV) and (VII), Ar³ is a divalent aromatic, adivalent aliphatic, or a divalent heterocyclic group. Examples of Ar³include but are not limited to:

wherein X² is —O—, —S—, —C(CF₃)₂—, —C(CH₃)₂—, —CH₂—, —SO₂—, or —NHCO—.

In Structure (VII), W is C(O)Cl, COOH or C(O)OR² wherein R² is C₁-C₇linear or branched alkyl group or a C₅-C₈ cycloalkyl group. Examples ofR² include, but are not limited to, —CH₃, —C₂H₅, n-C₃H₇, i-C₃H₇, n-C₄H₉,t-C₄H₉, and cyclohexyl.

Monomers having the Structure (VII) are diacids, diacid dichlorides anddiesters. Examples of suitable dicarboxylic acids (W═COOH) include, butare not limited to, 4,4′-diphenyletherdicarboxylic acid, terephthalicacid, isophthalic acid and mixtures thereof. Examples of suitable diacidchlorides (W═COCl) include, but are not limited to, isophthaloylchloride, phthaloyl dichloride, terphthaloyl dichloride,1,4-oxydibenzoyl chloride and mixtures thereof. Examples of suitabledicarboxylic esters (W═C(O)OR²) include, but are not limited to:dimethylisophthalate, dimethylphthalate, dimethylterphthalate,diethylisophthalate, diethylphthalate, diethylterphthalate and mixturesthereof.

Monomers having Structures (V) and (VI) and (VII) react to produce apolybenzoxazole precursor base polymer of Structure (I). Anyconventional method for reacting a dicarboxylic acid or its dichlorideor diester with at least one aromatic and/or heterocyclicdihydroxydiamine, and optionally, with at least one diamine, may beused. Generally, the reaction for diacid dichlorides (W═C(O)Cl) iscarried out at about −10° C. to about 30° C. for about 6 to about 48hours in the presence of an approximately stoichiometric amount of aminebase. Examples of suitable amine bases include, but are not limited topyridine, triethyl amine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),1,5-diazabicyclo[4.3.0]non-5-ene (DBN), dimethyl pyridine, anddimethylaniline. The polybenzoxazole precursor base polymer of Structure(I) may be isolated by precipitation into water, recovered by filtrationand dried. Descriptions of suitable syntheses employing diesters ordiacids may be found in U.S. Pat. Nos. 4,395,482, 4,622,285, and5,096,999, herein incorporated by reference.

The preferred reaction solvents are N-methyl-2-pyrrolidone (NMP),gamma-butyrolactone (GBL), N,N-dimethylformamide (DMF),N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone, dimethylsulfoxide(DMSO), sulfolane, and diglyme. The most preferred solvents areN-methyl-2-pyrrolidone (NMP) and gamma-butyrolactone (GBL).

Monomers having structure (V), (VI), and (VII) are employed such thatthe ratio of [(V)+(VI)]/(VII) is generally from about 1 to about 1.2.Preferably, the ratio of [(V)+(VI)]/(VII) is generally from about 1 toabout 1.1. The monomer having the Structure (V) is employed from about10 to about 100 mole % of [(V)+(VI)] and the monomer having Structure(VI) is employed from about 0 to about 90 mole % of [(V)+(VI)].Distribution of the polymeric units resulting from monomers having theStructures (V) and (VI) in the polybenzoxazole precursor base polymermay be random or in blocks within it.

In Structures (II) to (IV) x is an integer from about 10 to about 1000,y is an integer from about 0 to about 900 and (x+y) is about less then1000. A preferred range for x is from about 10 to about 300 and apreferred range for y is from about 0 to about 250. A more preferredrange for x is from about 10 to about 100 and a more preferred range fory is from about 0 to about 100. The most preferred range for x is fromabout 10 to about 50 and a most preferred range for y is from about 0 toabout 5.

The amount of (x+y) can be calculated by dividing the numeric averagemolecular weight (Mn) of a polymer of Structure (I) by the averagemolecular weight of the repeat unit. The value of Mn can be determinedby such standard methods as membrane osmometry or gel permeationchromatography as described, for example, in Jan Rabek, ExperimentalMethods in Polymer Chemistry, John Wiley & Sons, New York, 1983.

It should be noted that molecular weight and inherent viscosity of thepolymers and therefore, x and y at a constant stoichiometry, can have awide range depend on the reaction conditions such as the purity of thesolvent, the humidity, presence or absence of a blanket of nitrogen orargon gas, reaction temperature, reaction time, and other variables.

Polybenzoxazole precursor polymer of Structure (II) may be synthesizedby reaction of the polybenzoxazole precursor polymer of Structure (I)with about 1% to about 40 mole % of a diazoquinone (based on the numberof OH groups from the monomer of Structure (I)) in the presence of abase to yield the polybenzoxazole precursor of Structure (II) accordingto Reaction 1.

wherein Ar¹, Ar², Ar³, Ar⁴, D, k¹, k², x and y are as previouslydefined.

Examples of the diazoquinone compound DCl that can be reacted with thePBO polymer (I) include but are not limited to one of the following:

wherein, R is H, a halogen, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group,cyclopentyl or cyclohexyl. Examples of suitable R groups include, butare not limited to, methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, t-butyl, cyclopentyl t or cyclohexyl.

Generally, the reaction is carried out at about 0° C. to about 30° C.for about 3 to about 24 hours in a solvent in the presence of a base.Generally, a slight excess of base to DCl is employed. Examples of basesinclude but are not limited to amine bases such as pyridine,trialkylamine, methylpyridine, lutidine, n-methylmorpholine, and thelike. The most preferred base is triethylamine. The preferred reactionsolvents are tetrahydrofuran, acetone, N-methyl-2-pyrrolidone (NMP),gamma-butyrolactone (GBL), N,N-dimethylformamide (DMF),N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone, dimethylsulfoxide(DMSO), sulfolane, and diglyme. The most preferred reaction solvents aretetrahydrofuran and acetone. The reaction mixture should be protectedfrom actinic rays.

The molar amount of DCl may range from about 1% to about 40% of thequantity of OH groups from monomers of Structure (V) to yield k¹ from0.01 to about 0.4. A preferred amount of DCl is from about 1% to about20% of the quantity of OH groups from monomers of Structure (V) toproduce k¹ from about 0.01 to about 0.20. A more preferred amount of DClis from about 1% to about 10% of the quantity of OH groups from monomersof Structure (V) to produce k¹ from about 0.01 to about 0.10. A mostpreferred amount of DCl is from about 1% to about 5% of the quantity ofOH groups from monomers of Structure (V) to produce k¹ from about 0.01to about 0.05.

Polybenzoxazole precursor polymers of the following Structure (III):

wherein Ar¹ is a tetravalent aromatic group, a tetravalent heterocyclicgroup, or mixtures thereof; Ar² is a divalent aromatic, a divalentheterocyclic, a divalent alicyclic, or a divalent aliphatic group thatmay contain silicon; Ar³ is a divalent aromatic group, a divalentaliphatic group, a divalent heterocyclic group, or mixtures thereof; Ar⁴is Ar¹(OD)_(k) ¹(OH)_(k) ² or Ar² and G is a monovalent organic grouphaving a carbonyl, carbonyloxy or sulfonyl group may be synthesized byreaction of polybenzoxazole base polymer of Structure (I) with G-M whereG is a monovalent organic group having a carbonyl, carbonyloxy orsulfonyl group and M is a reactive leaving group. Examples of G include,but are not limited to the following structures:

Examples of M groups include, but are not limited to, Cl, Br, mesylate,triflate, substituted carbonyloxy groups, and substituted carbonategroups.

Examples of suitable classes of G-M compounds includes but are notlimited to carbon and sulfonic acid chlorides, carbon and sulfonic acidbromides, linear and cyclic carbon and sulfonic acid anhydrides, andalkoxy or aryloxy substituted acid chlorides. Examples of suitable G-Mcompounds include maleic anhydride, succinic anhydride, aceticanhydride, propionic anhydride, norbornene anhydride, phthalicanhydride, camphor sulfonic acid anhydride, trifluoromethane sulfonicacid anhydride, methanesulfonic acid anhydride, p-toluenesulfonic acidanhydride, ethanesulfonic acid anhydride, butanesulfonic acid anhydride,perfluorobutanesulfonic acid anhydride, acetyl chloride, methanesulfonylchloride, trifluoromethanesulfonyl chloride, benzoyl chloride,norbornene carboxylic acid chloride, di-t-butyl dicarbonate, dimethyldicarbonate, diethyldicarbonate, dibutyldicarbonate, t-butylchloroformate, ethyl chloroformate, n-butyl chloroformate, and methylchloroformate. Further examples include compounds having the structuresshown below.

The reaction can be carried out in a suitable solvent by addition of G-Mto a dry solution of the polybenzoxazole precursor base polymer at atemperature from about −25° C. to about 40° C. The more preferredtemperature is from about 0° C. to about 25° C. The most preferredtemperature is from about 5° C. to about 10° C. The reaction time isfrom about 1 hour to about 24 hours. The molar amount of GM employed isa slightly excess (3-6%) of the sum of the molar amounts of monomer ofstructures (V) and (VI) less the molar amount of monomer of structure(VII). Addition of organic or inorganic base may also be employed.Examples of suitable organic amine bases include, but are not limited topyridine, triethyl amine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),1,5-diazabicyclo[4.3.0]non-5-ene (DBN), dimethyl pyridine, anddimethylaniline. Examples of other suitable bases include sodiumhydroxide, sodium carbonate, and sodium silicate.

The preferred reaction solvents are propyleneglycolmethylether acetate(PGMEA), N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone (GBL),N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc),dimethyl-2-piperidone, dimethylsulfoxide (DMSO), tetrahydrofuran (THF),acetone, sulfolane, and diglyme. The most preferred solvents are diglymeand PGMEA.

Polybenzoxazole precursor polymer of Structure (IV) may be synthesizedby reaction of polybenzoxazole precursor polymer of Structure (III) withabout 1% to about 40% mole % of a diazoquinone (based on the number ofOH groups from the monomer of Structure (III) in the presence of a baseto yield the polybenzoxazole precursor (IV) according to Reaction 2.

wherein Ar¹, Ar², Ar³, Ar⁴, D, k¹, k², x, y, and G are as previouslydefined.

Examples of the diazoquinone compound DCl that can be reacted with thePBO polymer (III) include but are not limited to one of the following:

wherein, R is H, a halogen, a C₁-C₄ alkyl group, C₁-C₄ alkoxy group,cyclopentyl or cyclohexyl. Examples of suitable R groups include, butare nor limited to, methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, t-butyl, cyclopentyl or cyclohexyl.

The molar amount of DCl may range from about 1% to about 40% of thequantity of OH groups from monomers of Structure (V) to yield k¹ from0.01 to about 0.4. A preferred amount of DCl is from about 1% to about20% of the quantity of OH groups from monomers of Structure (V) toproduce k¹ from about 0.01 to about 0.20. A more preferred amount of DClis from about 1% to about 10% of the quantity of OH groups from monomersof Structure (V) to produce k¹ from about 0.01 to about 0.10. A mostpreferred amount of DCl is from about 1% to about 5% of the quantity ofOH groups from monomers of Structure (V) to produce k¹ from about 0.01to about 0.05.

The reaction conditions are identical to that description for thesynthesis of polybenzoxazole precursor polymer of Structure (II).

A polybenzoxazole precursor polymer of Structure (IV) can also beprepared by reaction of a polybenzoxazole precursor polymer of Structure(II) with G-M. The definition of G and M are as defined before and thereaction condition is the same as described for the preparation ofpolybenzoxazole precursor polymer of Structure (III).

The photoactive compound (b) of the photosensitive resin composition arethose of the following compounds (VIII) and comprises one or morediazonaphthoquinone photoactive compounds which are the condensationproducts of compounds containing from 2 to about 9 aromatic hydroxylgroups with a 5-naphthoquinone diazide sulfonyl compound and a4-naphthoquinone diazide sulfonyl compound.

The phenolic compounds (i.e. the backbone) typically employed in thepreparation of a photoactive compound may be prepared by any suitablemethod. A common method of syntheis is by reaction of a suitable phenolderivative with a suitable aldehyde or ketone in the presence of asolvent such as methanol. The reaction is most often catalyzed by astrong acid (e.g. sulfuric acid or p-toluene sulfonic acid). Generally,the reaction is carried out at about at about 15° C. to about 80° C. forabout 3 hours to about 48 hours.

The photoactive compounds (VIII) are synthesized by reaction of thebackbone with DCl. Generally, the reaction is carried out at about 0° C.to about 30° C. for about 4 to about 36 hours in a solvent in thepresence of a base. Generally, a slight excess of base to DCl isemployed. Examples of bases include but are not limited to amine basessuch as pyridine, trialkylamine, methylpyridine, lutidine,n-methylmorpholine, and the like. The most preferred base istriethylamine. The preferred reaction solvents are tetrahydrofuran(THF), gamma-butyrolactone (GBL), N,N-dimethylformamide (DMF), acetone,N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone, dimethylsulfoxide(DMSO), sulfolane, and diglyme. The most preferred solvents aretetrahydrofuran (THF), acetone and gamma-butyrolactone (GBL). Thereaction mixture should be protected from actinic rays.

Examples of compounds (VIII) include, but are not limited to, one ormore of the following compounds:

wherein at least one Q is (IX) and another Q is (X) with any remainderbeing H.

The ratio of (IX)/(X) is from about 1/99 to about 99/1. A preferredratio of (IX)/(X) is from about 20/80 to about 80/20. In compound VIII,Q=H may be from about 0% to about 90%. A preferred compound VIII iswhere Q=H is from about 0 to about 75%. A more preferred VIII is whereQ=H is from about 0 to about 50%. A most preferred VIII is where Q=H isfrom about 2% to about 34%.

The diazonaphthoquinone photoactive compound which comprises thecondensation product of a compound containing from 2 to about 9 aromatichydroxyl groups with a 5-naphthoquinone diazide sulfonyl compound and a4-naphthoquinone diazide sulfonyl compound may further contain similarcondensation products containing only a 5-naphthoquinone diazidesulfonyl moiety (moieties) or only a 4-naphthoquinone diazide sulfonylmoiety (moieties).

Suitable solvents of this photosensitive composition are polar organicsolvents. Suitable examples of polar organic solvents include but arenot limited to, N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone (GBL),N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone,N,N-dimethylformamide (DMF), and mixtures thereof. The preferredsolvents are gamma-butyrolactone and N-methyl-2-pyrrolidone. The mostpreferred solvent is gamma-butyrolactone.

The amount of polybenzoxazole precursor polymers of Structures (II) or(IV) in the photosensitive composition is from about 5 wt. % to about 50wt. %. The more preferred amount of polybenzoxazole precursor polymersof Structures (II) or (IV) is from about 20 wt. % to about 45 wt. % andthe most preferred amount of polybenzoxazole precursor polymers ofStructures (II) or (IV) is from about 30 wt. % to about 40 wt. %.Polybenzoxazole precursor polymers of Structures (II) or (IV) can beused singly or be combined in any ratio. Up to 25% of the amount of thepolybenzoxazole precursor polymer of Structures (II) or (V) may bereplaced by other organic solvent soluble, aqueous base soluble,aromatic or heterocyclic group polymers or copolymers. Examples oforganic solvent soluble, aqueous base soluble, aromatic or heterocyclicgroup polymers or copolymers may include polyimides,polybenzoimidazoles, polybenzothiazoles, polytrizoles, polyquinazolones,polyquinazolindiones, polyquinacridones, polybenxazinones,polyanthrazolines, polyoxadiazoles, polyhydantoins, polyindophenazines,or polythiadiazoles.

The amount of photosensitive compound, i.e., diazoquinone compound(VIII), used in this composition is from about 1 wt. % to about 20 wt. %of the total weight of the composition, preferably, about 2 wt. % to 10wt. %, and most preferably, about 3 wt. % to about 6 wt. %.

The solvent component (c) comprises about 40 wt. % to about 80 wt. % ofthe photosensitive composition. A preferred solvent range is from about45 wt. % to about 70 wt. %. A more preferred range of solvent is fromabout 50 wt. % to about 65 wt. %.

Optionally, an adhesion promoter may be included in the photosensitivecomposition. If employed, the amount of adhesion promoter ranges fromabout 0.1 wt. % to about 2 wt. % of total weight of composition. Apreferred amount of adhesion promoter is from about 0.2 wt. % to about1.5 wt. %. A more preferred amount of adhesion promoter is from about0.3 wt. % to about 1 wt. %. Suitable adhesion promoters include, forexample, amino silanes, and mixtures or derivatives thereof. Examples ofsuitable adhesion promoters which may be employed in the invention maybe described by Structure XI

wherein each R¹⁰ is independently a C₁-C₄ alkyl group or a C₅-C₇cycloalkyl group and each R¹¹ is independently a C₁-C₄ alkyl group, aC₁-C₄ alkoxy group, a C₅-C₇ cycloalkyl group or a C₅-C₇ cycloalkoxygroup; d is an integer from 0 to 3 and n is an integer from 1 to about6. R¹² is one of the following moieties:

wherein each R¹³ and R¹⁴ are independently a C₁-C₄ alkyl group or aC₅-C₇ cycloalkyl group, and R¹⁵ is a C₁-C₄ alkyl group and a C₅-C₇cycloalkyl group. Preferred adhesion promoters are those wherein R¹² are

More preferred adhesion promoters are those wherein R¹² is

The most preferred adhesion promoters are

The photosensitive compositions of the present invention may furtherinclude other additives. Suitable additives include, for example,leveling agents, dissolution inhibitors and the like. Such additives maybe included in the photosensitive compositions in about 0.03 to about 10wt % of the total weight of composition.

The second embodiment of the present invention concerns a process forforming a relief pattern using the photosensitive composition. Theprocess comprises the steps of:

-   -   (a) coating on a suitable substrate, a positive-working        photosensitive composition comprising one or more        polybenzoxazole precursor polymers having Structures (II) or        (IV), a diazonaphthoquinone photoactive compound which is the        condensation product of a compound containing from 2 to about 9        aromatic hydroxyl groups with a 5-naphthoquinone diazide        sulfonyl compound and a 4-naphthoquinone diazide sulfonyl        compound, and at least one solvent, thereby forming a coated        substrate;    -   (b) prebaking the coated substrate;    -   (c) exposing the prebaked coated substrate to actinic radiation;    -   (d) developing the exposed coated substrate with an aqueous        developer, thereby forming an uncured relief image on the coated        substrate; and    -   (e) baking the developed coated substrate at an elevated        temperature, thereby curing the relief image.

The process may optionally include the step of post exposure baking theexposed coated substrate at an elevated temperature, prior todeveloping. Still another optional step is rinsing the developedsubstrate, prior to curing.

The positive acting, photoactive resin of this invention is coated on asuitable substrate. The substrate may be, for example, semiconductormaterials such as a silicon wafer or a ceramic substrate, glass, metal,or plastic. Coating methods include, but are not limited to spraycoating, spin coating, offset printing, roller coating, screen printing,extrusion coating, meniscus coating, curtain coating, and immersioncoating. The resulting film is prebaked at an elevated temperature. Thebake may be completed at one or more temperatures within the temperaturebake of from about 70° C. to about 120° C. for several minutes to halfan hour, depending on the method, to evaporate the remaining solvent.Any suitable baking means may be employed. Examples of suitable bakingmeans include, but are not limited to, hot plates and convection ovens.The resulting dry film has a thickness of from about 3 to about 50micron or more preferably from about 4 to about 20 micron or mostpreferably from about 5 to about 15 micron.

After the bake, step, the resulting dry film is exposed to actinic raysin a preferred pattern through a mask. X-rays, electron beam,ultraviolet rays, visible light, and the like can be used as actinicrays. The most preferable rays are those with wavelength of 436 nm(g-line) and 365 nm (i-line).

Following exposure to actinic radiation, in an optional step it may beadvantageous to heat the exposed and coated substrate to a temperaturebetween about 70° C. and 120° C. The exposed and coated substrate isheated in this temperature range for a short period of time, typicallyseveral seconds to several minutes and may be carried out using anysuitable heating means. Preferred means include baking on a hot plate orin a convection oven. This process step is commonly referred to in theart as post exposure baking.

Next, the film is developed using an aqueous developer and a reliefpattern is formed. The aqueous developer contains aqueous base. Examplesof suitable bases include, but are not limited to, inorganic alkalis(e.g., potassium hydroxide, sodium hydroxide, ammonia water), primaryamines (e.g., ethylamine, n-propylamine), secondary amines (e.g.diethylamine, di-n-propylamine), tertiary amines (e.g., triethylamine),alcoholamines (e.g. triethanolamine), quaternary ammonium salts (e.g.,tetramethylammonium hydroxide, tetraethylammonium hydroxide), andmixtures thereof. The concentration of base employed will vary dependingon the base solubility of the polymer employed and the specific baseemployed. The most preferred developers are those containingtetramethylammonium hydroxide (TMAH). Suitable concentrations of TMAHrange from about 1% to about 5%. In addition, an appropriate amount of asurfactant can be added to the developer. Development can be carried outby means of immersion, spray, puddle, or other similar developingmethods at temperatures from about 10° C. to about 40° C. for about 30seconds to about 5 minutes. After development, the relief pattern may beoptionally rinsed using deionized water and dried by spinning, baking ona hot plate, in an oven, or other suitable means.

The benzoxazole ring is then formed by curing of the uncured reliefpattern to obtain the final high heat resistant pattern. Curing isperformed by baking the developed, uncured relief pattern at or abovethe glass transition temperature T_(g) of the photosensitive compositionto obtain the benzoxazole ring that provides high heat resistance.Typically, temperatures above about 200° C. are used.

Preferably, temperatures from about 250° C. to about 400° C. areapplied. The curing time is from about 15 minutes to about 24 hoursdepending on the particular heating method employed. A more preferredrange for the curing time is from about 20 minutes to about 5 hours andthe most preferred range of curing time is from about 30 minutes toabout 3 hours. Curing can be done in air or preferably, under a blanketof nitrogen and may be carried by any suitable heating means. Preferredmeans include baking on a hot plate or in a convection oven.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1 to 4 are graphs of exposure versus film thickness loss forcompositions of this invention and comparative compositions.

To illustrate the present invention, the following examples areprovided. It should be understood that the present invention is notlimited to the examples described.

SYNTHESIS EXAMPLE 1 Synthesis of Polybenzoxazole Precursor Polymer ofStructure (Ia)

To a 100 mL three-necked round bottom flask equipped with a mechanicalstirrer, nitrogen inlet and addition funnel, 3.66 g (10 mmol) ofhexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 1.70 g (21 mmol) ofpyridine and 15 g of N-methyl-2-pyrrolidone (NMP) were added. Thesolution was stirred at room temperature until all solids was dissolvedand then was cooled in an ice water bath at 0-5° C. To this solution,1.01 g (5 mmol) of isophthaloyl chloride and 1.477 g (5 mmol) of1,4-oxydibenzoyl chloride dissolved in 10 g of NMP was added drop-wise.After the addition was completed, the resulting mixture was stirred atroom temperature for 18 hours. The viscous solution was precipitated in800 mL of vigorously stirred de-ionized water. The polymer was collectedby filtration and washed with de-ionized water and a water/methanol(50/50) mixture. The polymer was dried under vacuum at 105° C. for 24hours. The yield was almost quantitative and the inherent viscosity ofthe polymer was 0.36 dL/g measured in NMP at the concentration of 0.5g/dL at 25° C.

SYNTHESIS EXAMPLE 2 Synthesis of Polymer of Structure (Ia) withAlternative Monomer Ratio

To a 2 L, three-necked, round bottom flask equipped with a mechanicalstirrer, nitrogen inlet and addition funnel, 155.9 g (426.0 mmol) ofhexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 64.3 g (794.9 mmol)of pyridine, and 637.5 g of N-methylpyrrolidone (NMP) were added. Thesolution was stirred at room temperature until all solids dissolved,then cooled in an ice water bath at 0-5° C. To this solution, 39.3 g(194 mmol) of isophthalyl chloride, and 56.9 g (194 mmol) of1,4-oxydibenzoyl chloride dissolved in 427.5 g of NMP, were addeddrop-wise. After the addition was completed, the resulting mixture wasstirred at room temperature for 18 hours. The viscous solution wasprecipitated in 10 liters of vigorously stirred de-ionized water. Thepolymer was collected by filtration and washed with de-ionized water anda water/methanol (50/50) mixture. The polymer was dried under vacuumconditions at 105° C. for 24 hours.

The yield was almost quantitative and the inherent viscosity (iv) of thepolymer was 0.20 dL/g measured in NMP at a concentration of 0.5 g/dL at25° C.

The number average molecular weight (Mn) was determined by gelpermeation chromatography using four Phenogel 10 columns with pore sizesof 10⁴ A, 500 A, 100 A and 50 A and THF as an eluent. Polystyrenestandards were used for calibration. The typical Mn for a polymerprepared by the above procedure was 5,800. The average molecular weightof the repeat unit is about 540, so the degree of polymerization (x+y)was determined to be about 11 (5800/540). Since y=0, X=11.

SYNTHESIS EXAMPLE 3 Synthesis of Polybenzoxazole Precursor Polymer ofStructure (IIa)

To a 100 mL three-necked round bottom flask equipped with a mechanicalstirrer, 5.42 g (10.0 mmol) of the polymer obtained in Synthesis Example1 and 50 mL of tetrahydrofuran (THF) were added. The mixture was stirredfor ten minutes and the solid was fully dissolved. 0.81 g (3 mmole) of5-naphthoquinone diazide sulfonyl chloride was then added and themixture was stirred for another 10 minutes. Triethylamine, 0.3 g (3mmol), was added gradually within 15 minutes and then the reactionmixture was stirred for 5 hours. The reaction mixture was then addedgradually to 500 mL of vigorously stirred de-ionized water. Theprecipitated product was separated by filtration and washed with 200 mLof de-ionized water. To the product was added another 600 mL de-ionizedwater and the mixture vigorously stirred for 30 minutes. Afterfiltration the product was washed with 100 mL de-ionized water. Theisolated product was dried at 40° C. overnight. The yield was 91%.

SYNTHESIS EXAMPLE 4 Synthesis of Polybenzoxazole Precursor Polymer ofStructure (IIa) Having Alternate Monomer Ratios

Synthesis Example 3 was repeated except the polymer obtained inSynthesis Example 2 was reacted with 3 mole % of 5-naphthoquinonediazide sulfonyl chloride. The inherent viscosity of the polymer was0.21 dL/g measured in NMP at the concentration of 0.5 g/dL at 25° C.

SYNTHESIS EXAMPLE 5 Synthesis of a Polybenzoxazole Precursor Polymer ofStructure (IIIa; G=acetyl)

3 small batches of PBO precursor polymers synthesized according toSynthesis Example 2 were mixed to obtain 100 g (184.5 mmol) PBOprecursor mixture with inherent viscosity of 0.205 dL/g. The mixture wasdissolved in 1000 g of diglyme. Residual water was removed as anazeotrope with diglyme using a rotary evaporator at 65° C. (10-12 torr).About 500 g of solvents was removed during the azeotrope distillation.

The reaction solution was transferred to a 1000 mL, three neck, roundbottom flask equipped with N₂ inlet and magnetic stirrer. The reactionmixture cooled on ice bath down to about 5° C. Acetyl chloride (3.3 ml,3.6 g) was added via syringe over the period of 5 min keeping reactionsolution well stirred.

The reaction was held on ice bath for about 10 min. Then the ice bathwas removed and the reaction was allowed to warm up over the period of 1hr. Then, the mixture was again cooled to 5° C. on the ice bath.Pyridine (3.7 ml, 3.6 g) was added via syringe over the period of 1 hr.Reaction was kept on the ice bath for 10 min, and then was allowed towarm up over the period of 1 hr.

The reaction mixture was precipitated into 6 L of water. The polymer wascollected by filtration and air dried overnight. Then, the polymer wasdissolved in 500-600 g of acetone and precipitated into 6 L ofwater/methanol (70/30). The polymer was again collected by filtrationand air-dried for several hours. The wet polymer cake was dissolved in amixture 700 g of THF and was precipitated in 7 L of water, filtered,air-dried overnight followed by 24 hr drying in vacuum oven at 90° C.

Terminal NH₂ groups have a chemical shift of 4.5 ppm. After the reactionof acetyl chloride and polybenzoxazole precursor polymer was completed,it was observed that this peak was completely vanished, indicative thatall NH₂ groups were reacted.

SYNTHESIS EXAMPLE 6 Synthesis of a Polybenzoxazole Precursor Polymer ofStructure (Iva); G=acetyl

To a 1 L three-necked round bottom flask equipped with a mechanicalstirrer, 67.5 g (approximately 120 mmol) of a mixture of two batches ofpolymer synthesized according to Synthesis Example 5 and 650 g oftetrahydrofuran (THF) were added. The mixture was stirred for tenminutes and the solid was fully dissolved. 1.01 g (0.38 mmole) of2,1-naphthoquinonediazide-5-sulfonyl chloride (IId R═H) was then addedand the mixture was stirred for another 10 minutes. Triethylamine, 0.39g (3.9 mmol) mixed with 50 mL THF was added gradually within 30 minutesand then the reaction mixture was stirred for overnight. The reactionmixture was then added gradually to 3 L of vigorously stirred de-ionizedwater. The precipitated product was separated by filtration andreslurried twice, each time with 3 L of de-ionized water. Afterfiltration the product was washed with 2 L de-ionized water. Theisolated product was dried at 40° C. overnight. The yield of product was84%.

SYNTHESIS EXAMPLE 7 Synthesis of a Polymer of Structure (IVb);G=phthaloyl Via an Alternative Embodiment

To a 1 L three-necked round bottom flask equipped with a mechanicalstirrer, and nitrogen inlet 100 g (165.9 mmol) of the polymer obtainedin Synthesis Example 4 and 290 g of diglyme were added. The mixture wasstirred for about 25 minutes and the solid was fully dissolved. 6.5 g(43.9 mmole) of phthalic anhydride was then added portion-wise within anhour at room temperature and the mixture was stirred for 16 hours. Thereaction mixture was then added gradually to 5200 mL of vigorouslystirred de-ionized water during a 60 minutes period. The precipitatedproduct was separated by filtration and washed with 2000 mL ofde-ionized water. To the product was added another 4000 mL de-ionizedwater and the mixture vigorously stirred for 30 minutes. Afterfiltration the product was washed with 2000 mL de-ionized water. Theisolated product was dried at 40° C. overnight. The yield of product was90%.

SYNTHESIS EXAMPLE 8 Preparation of Polybenzoxazole Precursor Polymer ofStructure (Ib)

To a 20 L reactor equipped with a mechanical agitator, nitrogen inletand thermocouple, 1500 g (4.09 mol) ofhexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 622 g (7.86 mol) ofpyridine and 7250 g of N-methyl-2-pyrrolidone (NMP) were added. Thesolution was stirred at room temperature until all solids dissolved andthen cooled in an ice water bath at 0-5° C. To this solution, 291 g g(1.43 mol) of terephthaloyl chloride and 634.5 g (2.15 mol) of1,4-oxydibenzoyl chloride dissolved in 2760 g of NMP was added by usinga diaphragm pump and Teflon transfer lines. The pump and Teflon transferlines were cleaned by using 200 g of NMP. After the addition wascompleted, the resulting mixture was stirred at room temperature for 18hours. The viscous solution was precipitated in 140 L of vigorouslystirred de-ionized water. The polymer was collected by filtration andwashed with 35 L of de-ionized water and a water/methanol (50/50)mixture. The polymer was dried under vacuum at 75° C. for 24 hours. Theyield was almost quantitative and the inherent viscosity of the polymerwas 0.183 dL/g measured in NMP at the concentration of 0.5 g/dL at 25°C.

SYNTHESIS EXAMPLE 9 Preparation of a Polybenzoxazole Precursor Polymerof Structure (IIb)

Synthesis Example 3 was repeated except the polymer from SynthesisExample 8 was employed and the ratio of2,1-naphthoquinonediazide-5-sulfonyl chloride to the total number of OHgroups of the polymer was changed to 0.02. The yield was 96% and theinherent viscosity of the polymer was 0.201 dL/g measured in NMP at theconcentration of 0.5 g/dL at 25° C.

SYNTHESIS EXAMPLE 10 Synthesis of Polymer of Structure (IIIb); G=Acetyl

Synthesis Example 5 was repeated except the polymer employed was the oneprepared in Synthesis Example 8. The yield was 83.7% and the inherentviscosity of the polymer was 0.205 dL/g measured in NMP at theconcentration of 0.5 g/dL at 25° C.

SYNTHESIS EXAMPLE 11 Synthesis of Polymer of Structure (IVb); G=Acetyl

Synthesis Example 4 was repeated except the polymer used was onesynthesized in Synthesis Example 10 and the ratio of2,1-naphthoquinonediazide-5-sulfonyl chloride (lid R═H) to OH groups ofthe polymer was changed to 2.0/100. The yield was 96% and the inherentviscosity of the polymer was 0.204 dL/g measured in NMP at theconcentration of 0.5 g/dL at 25° C.

SYNTHESIS EXAMPLE 12 Preparation of a Polybenzoxazole Precursor Polymerof Structure (Ic)

To a 20 L reactor equipped with a mechanical agitator, nitrogen inletand thermocouple, 1500 g (4.09 mol) ofhexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 622 g (7.86 mol) ofpyridine and 5000 g of N-methyl-2-pyrrolidone (NMP) were added. Thesolution was stirred at room temperature until all solids dissolved andthen cooled in an ice water bath at 0-5° C. To this solution, 212.09 g(1.04 mol) of terephthaloyl chloride, 212.0 g g (1.04 mol) ofisophthaloyl chloride and 411.0 g (1.39 mol) of 1,4-oxydibenzoylchloride dissolved in 2960 g of NMP were added by using a diaphragm pumpand Teflon transfer lines. The pump and Teflon transfer lines werecleaned using 200 g of NMP, which was then added to the solution. Afterthe addition was completed, the resulting mixture was stirred at roomtemperature for 18 hours. The viscous solution was precipitated in 140 Lof vigorously stirred de-ionized water. The polymer was collected byfiltration and washed with 35 L of de-ionized water and a water/methanol(50/50) mixture. The polymer was dried under vacuum at 75° C. for 24hours. The yield was almost quantitative and the inherent viscosity ofthe polymer was 0.205 dL/g measured in NMP at the concentration of 0.5g/dL at 25° C.

SYNTHESIS EXAMPLE 13 Synthesis of a Polybenzoxazole Polymer Precursor ofStructure (IIc)

Synthesis Example 3 was repeated except the polymer from SynthesisExample 12 was employed and the ratio of2,1-naphthoquinonediazide-5-sulfonyl chloride to the total number of OHgroups of the polymer was changed to 0.025. The yield was 96% and theinherent viscosity of the polymer was 0.201. dL/g measured in NMP at theconcentration of 0.5 g/dL at 25° C.

SYNTHESIS EXAMPLE 14 Synthesis of Polymer of Structure (IIIc); G=Acetyl

Synthesis Example 5 was repeated except the polymer used was oneprepared in Synthesis Example 12. The yield was 93.6% and the inherentviscosity of the polymer was 0.212 dL/g measured in NMP at theconcentration of 0.5 g/dL at 25° C.

SYNTHESIS EXAMPLE 15 Synthesis of Polymer of Structure (IVc); G=Acetyl

Synthesis Example 4 was repeated except the polymer employed was the oneprepared in Synthesis Example 14 and the ratio of2,1-naphthoquinonediazide-5-sulfonyl chloride (IId R═H) to OH groups ofthe polymer was changed to 3.0/100. The yield was 98.7% and the inherentviscosity of the polymer was 0.206 dL/g measured in NMP at theconcentration of 0.5 g/dL at 25° C.

SYNTHESIS EXAMPLE 16 Synthesis of a Photoactive Compound (PAC) ofStructure (VIII p)

To a 500 mL, 3-neck flask equipped with mechanical stirrer, droppingfunnel, pH probe, thermometer and nitrogen purge system were added 225mL of THF and 30 g of (4,4′-(1-phenylethylidene)bisphenol), BisphenolAP. The mixture was stirred until bisphenol AP was fully dissolved. Tothis was added 27.75g of 4-naphthoquinone diazide sulfonyl chloride and25 mL of THF. The reaction mixture was stirred until the solid was fullydissolved. 10.475 g of triethylamine dissolved in 50 mL THF was added tothe reaction mixture gradually while the pH was kept under 8 during thisprocess. The temperature during this exothermic reaction was kept under30° C. Upon completion of addition, the reaction mixture was stirred for48 hours. To this was added 27.75 g of 5-naphthoquinone diazide sulfonylchloride and 25 mL of THF and the reaction mixture was stirred for 30minutes. 10.475 g triethylamine dissolved in 50 mL THF was added to thereaction mixture gradually while the pH was kept under 8 during thisprocess. Again during this exothermic reaction the temperature was keptunder 30° C. Upon completion of the addition, the reaction mixture wasstirred for 20 hours. The reaction mixture was then added gradually to amixture of 6 L of Dl-water and 10 g of HCl. The product was filtered andwashed with 2 L of de-ionized water. The product was then reslurried byusing 3 L of de-ionized water, filtered and washed with 1 L Ofde-ionized water. The product was then dried inside a vacuum oven at 40°C. until the amount of water dropped below 2%. HPLC analysis revealedthat the product is mixture of several esters as shown in Table 1.

SYNTHESIS EXAMPLE 17 Synthesis of a Photoactive Compound (PAC) ofStructure (VIII p) Using Different Ratio of 4-naphthoquinone DiazideSulfonyl Chloride to 5-naphthoquinone Diazide Sulfonyl Chloride

Synthesis example 16 was repeated except the ratio of 4-naphthoquinonediazide sulfonyl chloride to 5-naphthoquinone diazide sulfonyl chloridewas changed from 1/1 to 1/3. HPLC analysis revealed that the product ismixture of several esters as shown in Table 1. The total yield of thisreaction was 91.7%

SYNTHESIS EXAMPLE 18 Synthesis of a Photoactive Compound (PAC) ofStructure (VIII p) Using Different Ratio of 4-naphthoquinone DiazideSulfonyl Chloride to 5-naphthoquinone Diazide Sulfonyl Chloride

Synthesis Example 16 was repeated except the ratio of 4-naphthoquinonediazide sulfonyl chloride to 5-naphthoquinone diazide sulfonyl chloridewas changed from 1/1 to 3/1. HPLC analysis revealed that the product ismixture of several esters as shown in Table 1. The total yield of thisreaction was 88.0%. TABLE 1 Example Example Exam- Structure Compound 1617 ple 18

S214 0.61% 0.12 0.21

S215 0.53% 0.26 0.11

S214 monoester 1.72% 0.30 2.73

S215 monoester 1.4% 0.62 0.68

S215 diester 18.9% 50.3 4.50

Mixed Ester PAC 46.7% 39.9 32.6

S214 diester 29% 8.00 58.3The solubility of this compound on GBL was tested and it was more than18%

COMPARATIVE SYNTHESIS EXAMPLE 1 Synthesis of a Photoactive Compound(PAC) of Structure (XII)

The reaction was similar to that of Example 17 except only5-naphthoquinone diazide sulfonyl chloride was used. HPLC analysisrevealed that about 94% of the product was diester and 6% was monoester.The solubility of this compound in GBL was about 10%

COMPARATIVE SYNTHESIS EXAMPLE 2 Synthesis of a Photoactive Compound(PAC) of Structure (XIII)

The reaction was similar to that of Synthesis Example 17 except only4-naphthoquinone diazide sulfonyl chloride was used. HPLC analysisrevealed that about 87% of the product is diester and 13% is monoester.The solubility of this compound on GBL was tested and it was only about2-3%.

EXAMPLE 1 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

100 parts polymer obtained in Synthesis Example 4, 11.9 part of bisphenol AP PAC obtained from example 16, 5 parts of diphenylsilane dioland 3 parts of gamma-ureidopropyltrimethoxysilane (adhesion promoter)was dissolved in GBL and filtered. The formulation was spin coated on asilicon wafer then baked on a hotplate for 4 minutes at 120° C,resulting in a film thickness of 14.01 μm. The film was then exposedutilizing an i-line stepper in an open frame exposure array, whichincrementally increased exposure energy 10 mJ/cm² with a startingexposure energy of 400 mJ/cm². The wafer was then developed with two 50second puddles with a 0.262N aqueous solution of tetra-methyl ammoniumhydroxide, resulting in a array of exposed boxes that were either clearof or containing residue. These boxes were visually inspected for whatwas exposure energy at which residue were completely cleared from theexposed area. The formulation cleared boxes at a dose of 495 mJ/cm². Theunexposed film thickness decreased 6.15 microns to 7.85 microns (43.97%Film thickness loss).

EXAMPLE 2 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

The photosensitive composition of Example 1 was spin coated on a siliconwafer and baked on a hotplate for 4 minutes at 120° C., resulting in afilm thickness of 14.05 μm. The film was then exposed utilizing ani-line stepper in an open frame exposure array, which incrementallyincreased exposure energy 10 mJ/cm² with a starting exposure energy of600 mJ/cm². The wafer was then developed with two 40 second puddles. Theformulation cleared boxes at a dose of 670 mJ/cm². The unexposed filmthickness decreased 5.13 microns to 8.92 microns (36.51% Film thicknessloss).

EXAMPLE 3 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

The photosensitive composition of Example 1 was spin coated on a siliconwafer then baked on a hotplate for 4 minutes at 120° C., resulting in afilm thickness of 14.03 μm. The film was then exposed utilizing ani-line stepper in an open frame exposure array, which incrementallyincreased exposure energy 10 mJ/cm² with a starting exposure energy of800 mJ/cm². The wafer was then developed with two 28 second puddles. Theformulation cleared boxes at a dose of 950 mJ/cm². The unexposed filmthickness decreased 3.98 microns to 10.05 microns (28.37% Film thicknessloss).

EXAMPLE 4 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

The photosensitive composition of Example 1 was spin coated on a siliconwafer then baked on a hotplate for 4 minutes at 120° C., resulting in afilm thickness of 13.91 μm. The film was then exposed utilizing ani-line stepper in an open frame exposure array, which incrementallyincreased exposure energy 50 mJ/cm² with a starting exposure energy of300 mJ/cm². The wafer was then developed with two 41.5 second puddles.The formulation cleared boxes at a dose of 650 mJ/cm². The unexposedfilm thickness decreased 5.33 microns to 8.58 microns (38.32% Filmthickness loss).

COMPARATIVE EXAMPLE 1 Lithographic Evaluation of a PhotosensitiveComposition Based on a PAC with Structure (XII)

100 parts polymer obtained in Synthesis Example 4, 11.9 part of bisphenol AP PAC shown in structure XII (see Comparative Synthesis Example1), 5 parst of diphenylsilane diol and 3 parts ofgamma-ureidopropyltrimethoxysilane (adhesion promoter) was dissolved inGBL and filtered. The formulation was spin coated on a silicon waferthen baked on a hotplate for 4 minutes at 120° C., resulting in a filmthickness of 14.17 μm. The film was then exposed utilizing an i-linestepper in an open frame exposure array, which incrementally increasedexposure energy 10 mJ/cm² with a starting exposure energy of 400 mJ/cm².The wafer was then developed with two 56 second puddles with a 0.262Naqueous solution of tetra-methyl ammonium hydroxide, resulting in aarray of exposed boxes that were either clear of or containing residue.These boxes were visually inspected for what was exposure energy atwhich residue were completely cleared from the exposed area. Theformulation cleared boxes at a dose of 440 mJ/cm². The unexposed filmthickness decreased 7.3 microns to 6.87 microns (51.52% Film thicknessloss).

COMPARATIVE EXAMPLE 2 Lithographic Evaluation of a PhotosensitiveComposition Based on a PAC with Structure (XII)

The photosensitive composition of Comparative Example 1 was spin coatedon a silicon wafer then baked on a hotplate for 4 minutes at 120° C.,resulting in a film thickness of 14.12 μm. The film was then exposedutilizing an i-line stepper in an open frame exposure array, whichincrementally increased exposure energy 10 mJ/cm² with a startingexposure energy of 600 mJ/cm². The wafer was then developed with two 42second puddles. The formulation cleared boxes at a dose of 640 mJ/cm².The unexposed film thickness decreased 5.68 microns to 8.44 microns(40.23% Film thickness loss).

COMPARATIVE EXAMPLE 3 Lithographic Evaluation of a PhotosensitiveComposition Based on a PAC with Structure (XII)

The photosensitive composition of Comparative Example 1 was spin coatedon a silicon wafer then baked on a hotplate for 4 minutes at 120° C.,resulting in a film thickness of 14.07 μm. The film was then exposedutilizing an i-line stepper in an open frame exposure array, whichincrementally increased exposure energy 10 mJ/cm² with a startingexposure energy of 800 mJ/cm². The wafer was then developed with two 34second puddles. The formulation cleared boxes at a dose of 825 mJ/cm².The unexposed film thickness decreased 4.82 microns to 9.25 microns(34.26% Film thickness loss).

COMPARATIVE EXAMPLE 4 Lithographic Evaluation of a PhotosensitiveComposition Based on a PAC with Structure (XII)

The photosensitive composition of Comparative Example 1 was spin coatedon a silicon wafer then baked on a hotplate for 4 minutes at 120° C.,resulting in a film thickness of 14.18 μm. The film was then exposedutilizing an i-line stepper in an open frame exposure array, whichincrementally increased exposure energy 50 mJ/cm² with a startingexposure energy of 300 mJ/cm². The wafer was then developed with two41.5 second puddles. The formulation cleared boxes at a dose of 700mJ/cm². The unexposed film thickness decreased 5.66 microns to 8.62microns (39.92% Film thickness loss).

The results of Example 1-4 and comparative Example of 1-4 are shown inFIG. 1. From these results it is obvious that the composition used inExamples 1-4 have a better film thickness retention at the same energydose in compare with the composition used in Comparative Examples 1-4.

EXAMPLE 5 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

100 parts polymer obtained in Synthesis Example 4, 11.9 part of bisphenol AP PAC obtained from example 17, 5 part of diphenylsilane dioland 3 parts of gamma-ureidopropyltrimethoxysilane was dissolved in GBLand filtered. The formulation was spin coated on a silicon wafer thenbaked on a hotplate for 4 minutes at 120° C., resulting in a filmthickness of 14.15 μm. The film was then exposed utilizing an i-linestepper in an open frame exposure array, which incrementally increasedexposure energy 20 mJ/cm² with a starting exposure energy of 300 mJ/cm².The wafer was then developed with two 45 second puddles with a 0.262Naqueous solution of tetra-methyl ammonium hydroxide, resulting in aarray of exposed boxes that were either clear of or containing residue.These boxes were visually inspected for what was exposure energy atwhich residue were completely cleared from the exposed area. Theformulation cleared boxes at a dose of 485 mJ/cm². The unexposed filmthickness decreased 6.71 microns to 7.43 microns (47.44% Film thicknessloss).

EXAMPLE 6 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

The photosensitive composition of Example 5 was spin coated on a siliconwafer and baked on a hotplate for 4 minutes at 120° C., resulting in afilm thickness of 14.11 μm. The film was then exposed utilizing ani-line stepper in an open frame exposure array, which incrementallyincreased exposure energy 20 mJ/cm² with a starting exposure energy of500 mJ/cm². The wafer was then developed with two 33 second puddles. Theformulation cleared boxes at a dose of 680 mJ/cm². The unexposed filmthickness decreased 5.30 microns to 8.81 microns (37.57% Film thicknessloss).

EXAMPLE 7 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

The photosensitive composition of Example 5 was spin coated on a siliconwafer then baked on a hotplate for 4 minutes at 120° C., resulting in afilm thickness of 14.14 μm. The film was then exposed utilizing ani-line stepper in an open frame exposure array, which incrementallyincreased exposure energy 20 mJ/cm² with a starting exposure energy of800 mJ/cm². The wafer was then developed with two 28 second puddles. Theformulation cleared boxes at a dose of 920 mJ/cm². The unexposed filmthickness decreased 4.19 microns to 9.95 microns (29.63% Film thicknessloss).

The results of Example 5-7 and comparative Example of 1-4 are shown inFIG. 2. From these results it is obvious that the composition used inExamples 5-7 have a better film thickness retention at the same energydose in compare with the composition used in Comparative Examples 1-4.

EXAMPLE 8 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

100 parts polymer obtained in Synthesis Example 4, 11.9 part of bisphenol AP PAC obtained from example 18, 5 part of diphenylsilane dioland 3 parts of gamma-ureidopropyltrimethoxysilane was dissolved in GBLand filtered. The formulation was spin coated on a silicon wafer thenbaked on a hotplate for 4 minutes at 120° C., resulting in a filmthickness of 14.09 μm. The film was then exposed utilizing an i-linestepper in an open frame exposure array, which incrementally increasedexposure energy 20 mJ/cm² with a starting exposure energy of 800 mJ/cm².The wafer was then developed with two 22 second puddles with a 0.262Naqueous solution of tetra-methyl ammonium hydroxide, resulting in aarray of exposed boxes that were either clear of or containing residue.These boxes were visually inspected for what was exposure energy atwhich residue were completely cleared from the exposed area. Theformulation cleared boxes at a dose of 860 mJ/cm². The unexposed filmthickness decreased 4.06 microns to 10.02 microns (28.84% Film thicknessloss).

EXAMPLE 9 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

The photosensitive composition of Example 8 was spin coated on a siliconwafer and baked on a hotplate for 4 minutes at 120° C., resulting in afilm thickness of 14.09 μm. The film was then exposed utilizing ani-line stepper in an open frame exposure array, which incrementallyincreased exposure energy 20 mJ/cm² with a starting exposure energy of500 mJ/cm². The wafer was then developed with two 30 second puddles. Theformulation cleared boxes at a dose of 640 mJ/cm². The unexposed filmthickness decreased 5.11 microns to 8.99 microns (36.23% Film thicknessloss).

EXAMPLE 10 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

The photosensitive composition of Example 8 was spin coated on a siliconwafer then baked on a hotplate for 4 minutes at 120° C., resulting in afilm thickness of 14.11 μm. The film was then exposed utilizing ani-line stepper in an open frame exposure array, which incrementallyincreased exposure energy 20 mJ/cm² with a starting exposure energy of300 mJ/cm². The wafer was then developed with two 28 second puddles. Theformulation cleared boxes at a dose of 420 mJ/cm². The unexposed filmthickness decreased 6.66 microns to 7.45microns (47.21% Film thicknessloss).

The results of Example 8-10 and comparative Example of 1-4 are shown inFIG. 3. From these results it is obvious that the composition used inExamples 8-10 have a better film thickness retention at the same energydose in compare with the composition used in Comparative Examples 1-4.

EXAMPLE 11 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p).

100 parts polymer obtained in Synthesis Example 4, 14.3 parts of bisphenol AP PAC obtained from Synthesis Example 16, 2.5 parts ofdiphenylsilane diol and 1.4 parts of gamma-ureidopropyltrimethoxysilane(adhesion promoter) were dissolved in GBL and filtered. The formulationwas spin coated on a silicon wafer then baked on a hotplate for 4minutes at 120° C., resulting in a film thickness of 14.07 μm. The filmwas then exposed utilizing an i-line stepper in an open frame exposurearray, which incrementally increased exposure energy 50 mJ/cm² with astarting exposure energy of 300 mJ/cm². The wafer was then developedwith two 41.5 second puddles with a 0.262N aqueous solution oftetramethyl ammonium hydroxide, resulting in a array of exposed boxesthat were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 800 mJ/cm². The unexposed film thickness decreased 4.59 to9.48 microns (32.62% Film thickness loss).

COMPARATIVE EXAMPLE 5 Composition Based on a PAC with Structure (XIII)

Attempts to prepare a composition containing 100 parts polymer obtainedin Synthesis Example 4, 11.9 parts of bis phenol AP PAC shown instructure (XIII; see Comparative Synthesis Example 2), 5 parts ofdiphenylsilane diol and 3 parts of gamma-ureidopropyltrimethoxysilane(adhesion promoter) dissolved in GBL failed due to lack of solubility ofPAC (XIII).

EXAMPLE 12 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

100 parts polymer obtained in Synthesis Example 9, 21 parts PAC obtainedfrom Synthesis Example 16 and 1.5 part ofgamma-glycidoxypropyltrimethoxysilane was dissolved in NMP and filtered.The formulation was spin coated on a silicon wafer then baked on ahotplate for 4 minutes at 120° C., resulting in a film thickness of14.21 μm. The film was then exposed utilizing an i-line stepper in anopen frame exposure array, which incrementally increased exposure energy25 mJ/cm² with a starting exposure energy of 700 mJ/cm². The wafer wasthen developed with two 40 second puddles with a 0.262N aqueous solutionof tetra-methyl ammonium hydroxide, resulting in a array of exposedboxes that were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 1100 mJ/cm². The unexposed film thickness decreased 6.85microns to 7.36 microns (48.21% Film thickness loss).

EXAMPLE 13 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

100 parts polymer obtained in Synthesis Example 13, 21 parts of PACobtained from Synthesis Example 16, 2.5 part of diphenylsilane diol and5 part of gamma-mercaptopropyltrmiethoxysilane was dissolved in NMP andfiltered. The formulation was spin coated on a silicon wafer then bakedon a hotplate for 4 minutes at 120° C., resulting in a film thickness of16.76 μm. The film was then exposed utilizing an i-line stepper in anopen frame exposure array, which incrementally increased exposure energy50 mJ/cm² with a starting exposure energy of 100 mJ/cm². The wafer wasthen developed with two 70 second puddles with a 0.262N aqueous solutionof tetra-methyl ammonium hydroxide, resulting in a array of exposedboxes that were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 500 mJ/cm². The unexposed film thickness decreased 9.72microns to 7.04 microns (57.98% Film thickness loss).

EXAMPLE 14 Lithographic Evaluation of a Photosensitive Composition Basedon a PAC with Structure (VIII p)

100 parts polymer obtained in Synthesis Example 7, 13.5 parts of PACobtained from Synthesis Example 16, 1.98 part of diphenylsilane diol and1.53 part of gamma-Ureidopropyltrimethoxysilane was dissolved in GBL andfiltered. The formulation was spin coated on a silicon wafer then bakedon a hotplate for 4 minutes at 120° C., resulting in a film thickness of13.99 μm. The film was then exposed utilizing an i-line stepper in anopen frame exposure array, which incrementally increased exposure energy10 mJ/cm² with a starting exposure energy of 440 mJ/cm². The wafer wasthen developed with two 30 second puddles with a 0.262N aqueous solutionof tetra-methyl ammonium hydroxide, resulting in a array of exposedboxes that were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 520 mJ/cm². The unexposed film thickness decreased 5.70microns to 8.29 microns (40.73% Film thickness loss).

SYNTHESIS EXAMPLE 19 Synthesis of a Photoactive Compound (PAC) ofStructure (VIIIo)

To a 500 mL, 3-neck flask equipped with mechanical stirrer, droppingfunnel, pH probe, thermometer and nitrogen purge system were added 150mL of THF and 15.14 g ofbis(3,5-dimethyl-4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane. Themixture was stirred until the backbone was fully dissolved. To this wasadded 9.028 g of 4-naphthoquinone diazide sulfonyl chloride and 10 mL ofTHF. The reaction mixture was stirred until the solid was fullydissolved. 3.732 g of triethylamine dissolved in 10 mL THF was added tothe reaction mixture gradually while the pH was kept under 8 during thisprocess. The temperature during this exothermic reaction was kept under30° C. Upon completion of addition, the reaction mixture was stirred for24 hours. At this point HPLC showed that 6.5% of S-214 was not reacted.To the mixture was added 2.5 g of triethylamine and 10 mL of THF. Uponcompletion of addition, the reaction mixture was stirred for another 24hours To this was added 16.76 g of 5-naphthoquinone diazide sulfonylchloride and 10 mL of THF and the reaction mixture was stirred for 30minutes. 5.0 g triethylamine dissolved in 10 mL THF was added to thereaction mixture gradually while the pH was kept under 8 during thisprocess. Again during this exothermic reaction the temperature was keptunder 30° C. Upon completion of the addition, the reaction mixture wasstirred for 20 hours. At this point HPLC showed that 4.9% of S-215 wasnot reacted. To the mixture was added 2.5 g of triethylamine and 10 mLof THF. Upon completion of addition, the reaction mixture was stirredfor another 24 hours. The reaction mixture was then added gradually to amixture of 4 L of DI-water and 10 g of HCl. The product was filtered andwashed with 1 L of de-ionized water. The product was then reslurried byusing 2.5 L of de-ionized water, filtered and washed with 1 L Ofde-ionized water. The product was then dried inside a vacuum oven at 40°C. until the amount of water dropped below 2%. HPLC analysis revealedthat the product was a mixture of esters as shown in Table 2. TABLE 2Structure Amount

2.41%

8.11%

10.48%

1.04%

32.09%

10.57%

28.1%

2.66

The total amount of DNQ on the backbone was about 2.22 mole per 1 moleof backbone. The composition of the reaction product was 10.5%monoesters, 43.6 diesters, and 41.33% triesters.

EXAMPLE 15 Lithographic Evaluation of a Photosensitive Composition Basedon PAC (VIIIo)

100 parts polymer obtained in Synthesis Example 4, 17 parts of PAC VIIIoobtained in Synthesis Example 19, and 1 part oftriethoxysilanepropylethylcarbamate were dissolved in GBL and filtered.The formulation was spin coated on a silicon wafer and then baked on ahotplate for 4 minutes at 120° C., resulting in a film thickness of14.02 μm. The film was then exposed utilizing an i-line stepper in anopen frame exposure array, which incrementally increased exposure energy20 mJ/cm² with a starting exposure energy of 300 mJ/cm². The wafer wasthen developed with two 20 second puddles with a 0.262N aqueous solutionof tetra-methyl ammonium hydroxide, resulting in a array of exposedboxes that were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 664 mJ/cm². The unexposed film thickness decreased 5.04microns to 8.97 microns (36.01% Film thickness loss).

EXAMPLE 16 Lithographic Evaluation of a Photosensitive Composition Basedon PAC (VIIIo)

The photosensitive composition of Example 15 was spin coated on asilicon wafer and then baked on a hotplate for 4 minutes at 120° C.,resulting in a film thickness of 13.89 μm. The film was then exposedutilizing an i-line stepper in an open frame exposure array, whichincrementally increased exposure energy 20 mJ/cm² with a startingexposure energy of 100 mJ/cm². The wafer was then developed with two 30second puddles with a 0.262N aqueous solution of tetra-methyl ammoniumhydroxide, resulting in a array of exposed boxes that were either clearof or containing residue. These boxes were visually inspected for whatwas exposure energy at which residue were completely cleared from theexposed area. The formulation cleared boxes at a dose of 364 mJ/cm². Theunexposed film thickness decreased 6.82 microns to 7.07 microns (49.13%Film thickness loss).

EXAMPLE 17 Lithographic Evaluation of a Photosensitive Composition Basedon PAC (VIIIo)

The photosensitive composition of Example 15 was spin coated on asilicon wafer and then baked on a hotplate for 4 minutes at 120° C.,resulting in a film thickness of 14.00 μm. The film was then exposedutilizing an i-line stepper in an open frame exposure array, whichincrementally increased exposure energy 20 mJ/cm² with a startingexposure energy of 100 mJ/cm². The wafer was then developed with two 35second puddles with a 0.262N aqueous solution of tetra-methyl ammoniumhydroxide, resulting in a array of exposed boxes that were either clearof or containing residue. These boxes were visually inspected for whatwas exposure energy at which residue were completely cleared from theexposed area. The formulation cleared boxes at a dose of 292 mJ/cm². Theunexposed film thickness decreased 7.52 microns to 6.47 microns (53.75%Film thickness loss).

EXAMPLE 18 Lithographic Evaluation of a Photosensitive Composition Basedon PAC (VIIIo)

Photosensitive composition of Example 15 was spin coated on a siliconwafer and then baked on a hotplate for 4 minutes at 120° C., resultingin a film thickness of 13.90 μm. The film was then exposed utilizing ani-line stepper in an open frame exposure array, which incrementallyincreased exposure energy 20 mJ/cm² with a starting exposure energy of600 mJ/cm². The wafer was then developed with two 15 second puddles witha 0.262N aqueous solution of tetra-methyl ammonium hydroxide, resultingin a array of exposed boxes that were either clear of or containingresidue. These boxes were visually inspected for what was exposureenergy at which residue were completely cleared from the exposed area.The formulation cleared boxes at a dose of 852 mJ/cm². The unexposedfilm thickness decreased 4.17 microns to 9.73 microns (30.00% Filmthickness loss).

COMPARATIVE SYNTHESIS EXAMPLE 3

Pac XIV was prepared by a method similar to that described inComparative Synthesis Example 1. Analysis (see Table 3) showed that itwas mixture composed of the following components. TABLE 3 StructureAmount

2.69%

27.60%

62.77%

The total amount of DNQ was 2.48 mole per 1 mole of backbone andcontained 2.69% monoester, 27.6% diester, and 62.77% triester. Triestersare more effective in retaining unexposed film during lithography.

COMPARATIVE EXAMPLE 6 Lithographic Evaluation of a PhotosensitiveComposition Based on PAC (XIV)

100 parts polymer obtained in Synthesis Example 4, 17 parts of PAC XIVobtained in Comparative Synthesis Example 3, and 1 part oftriethoxysilanepropylethylcarbamate were dissolved in GBL and filtered.The formulation was spin coated on a silicon wafer and then baked on ahotplate for 4 minutes at 120° C., resulting in a film thickness of14.31 μm. The film was then exposed utilizing an i-line stepper in anopen frame exposure array, which incrementally increased exposure energy20 mJ/cm² with a starting exposure energy of 100 mJ/cm². The wafer wasthen developed with two 70 second puddles with a 0.262N aqueous solutionof tetra-methyl ammonium hydroxide, resulting in a array of exposedboxes that were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 300 mJ/cm². The unexposed film thickness decreased 7.75microns to 6.56 microns (54.14% Film thickness loss).

COMPARATIVE EXAMPLE 7 Lithographic Evaluation of a PhotosensitiveComposition Based on PAC (XIV)

The photosensitive composition prepared in Comparative Example 6 wasspin coated on a silicon wafer and then baked on a hotplate for 4minutes at 120° C., resulting in a film thickness of 14.16 μm. The filmwas then exposed utilizing an i-line stepper in an open frame exposurearray, which incrementally increased exposure energy 20 m J/cm² with astarting exposure energy of 300 mJ/cm². The wafer was then developedwith two 60 second puddles with a 0.262N aqueous solution oftetra-methyl ammonium hydroxide, resulting in a array of exposed boxesthat were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 384 mJ/cm². The unexposed film thickness decreased 6.87microns to 7.29 microns (48.51% Film thickness loss).

COMPARATIVE EXAMPLE 8 Lithographic Evaluation of a PhotosensitiveComposition Based on PAC (XIV)

The photosensitive composition obtained in Comparative Example 6 wasspin coated on a silicon wafer and then baked on a hotplate for 4minutes at 120° C., resulting in a film thickness of 14.19 μm. The filmwas then exposed utilizing an i-line stepper in an open frame exposurearray, which incrementally increased exposure energy 20 m J/cm² with astarting exposure energy of 350 mJ/cm². The wafer was then developedwith two 50 second puddles with a 0.262N aqueous solution oftetra-methyl ammonium hydroxide, resulting in a array of exposed boxesthat were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 534 mJ/cm². The unexposed film thickness decreased 5.90microns to 8.29 microns (41.58% Film thickness loss).

COMPARATIVE EXAMPLE 9 Lithographic Evaluation of a PhotosensitiveComposition Based on PAC (XIV)

The photosensitive composition obtained in Comparative Example 6 wasspin coated on a silicon wafer and then baked on a hotplate for 4minutes at 120° C., resulting in a film thickness of 14.11 μm. The filmwas then exposed utilizing an i-line stepper in an open frame exposurearray, which incrementally increased exposure energy 20 m J/cm² with astarting exposure energy of 500 mJ/cm². The wafer was then developedwith two 40 second puddles with a 0.262N aqueous solution oftetra-methyl ammonium hydroxide, resulting in a array of exposed boxesthat were either clear of or containing residue. These boxes werevisually inspected for what was exposure energy at which residue werecompletely cleared from the exposed area. The formulation cleared boxesat a dose of 684 mJ/cm². The unexposed film thickness decreased 4.80microns to 9.30 microns (34.04% Film thickness loss).

The results of Examples 15-18 are compared with Comparative Examples 6-9in FIG. 4. This shows that although the total amount of DNQ is lower inthe mixed ester, surprisingly, the performance of the two photosensitivecompositions are similar. Lower DNQ amounts decrease costs ofmanufacture.

In addition, the present invention includes electronic parts obtained byusing the invention composition. The application of the saidpolybenzoxazole films in semiconductor industry include, but are notlimited to, stress relieve coatings for packaged semiconductors, alphaparticle barrier films, interlevel dielectrics, insulating films andpatterned engineering plastic layers. The examples of articles ofcommerce made using the disclosed formulation and method include, butnot limited to memory devices, such as DRAMs, logic devices, such asmicroprocessors or microcontrollers, plating stencils, etc.

While the invention has been described herein with reference to thespecific embodiments thereof, it will be appreciated that changes,modification and variations can be made without departing from thespirit and scope of the inventive concept disclosed herein. Accordingly,it is intended to embrace all such changes, modification and variationsthat fall with the spirit and scope of the appended claims.

1. A positive photosensitive resin composition comprising: (a) one ormore polybenzoxazole precursor polymers having any of the structures(II) or (IV);

wherein Ar¹ is selected from the group consisting of a tetravalentaromatic group, a tetravalent heterocyclic group, and mixtures thereof;Ar² is selected from the group consisting of a divalent aromatic, adivalent heterocyclic, a divalent alicyclic, and a divalent aliphaticgroup that may contain silicon; Ar³ is selected from the groupconsisting of a divalent aromatic group, a divalent aliphatic group, adivalent heterocyclic group, and mixtures thereof; Ar⁴ is selected fromthe group consisting of Ar¹(OD)_(k) ¹(OH)_(k) ² and Ar², x is from about10 to about 1000; y is from 0 to about 900; D is selected from the groupconsisting of one of the following moieties:

wherein R is selected from the group consisting of H, halogen, C₁-C₄alkyl group, C₁-C₄ alkoxy group, cyclopentyl and cyclohexyl; k¹ can beany positive value of up to about 0.5, k² can be any value from about1.5 to about 2 with the proviso that (k¹+k²)=2, G is a monovalentorganic group having a group selected from the group consisting ofcarbonyl, carbonyloxy and sulfonyl group, (b) a diazonaphthoquinonephotoactive compound which is the condensation product of a compoundcontaining from 2 to about 9 aromatic hydroxyl groups with a5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinonediazide sulfonyl compound, and (c) at least one solvent.
 2. A positivephotosensitive resin composition according to claim 1, wherein Ar¹ is amoiety selected from the group consisting of

wherein X¹ is selected from the group consisting of —O—, —S—, —C(CF₃)₂—,—CH₂—, —SO₂—, —NHCO— and —SiR⁹ ₂— and each R⁹ is independently selectedfrom the group consisting of a C₁-C₇ linear or branched alkyl and aC₅-C₈ cycloalkyl group.
 3. A positive photosensitive resin compositionaccording to claim 1, wherein Ar¹ is a moiety derived from a reactantselected from the group consisting of2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane,3,3′-dihydroxy-4,4′-diaminodiphenylether, 3,3′-dihydroxybenzidine,4,6-diaminoresorcinol, and 2,2-bis(3-amino4-hydroxyphenyl)propane andmixtures thereof.
 4. A positive photosensitive resin compositionaccording to claim 1, wherein Ar² is a moiety selected from the groupconsisting of

wherein X¹ is selected from the group consisting of —O—, —S—, —C(CF₃)₂—,—CH₂—, —SO₂—, —NHCO— and —SiR⁹ ₂— and each R⁹ is independently selectedfrom the group consisting of a C₁-C₇ linear or branched alkyl and aC₅-C₈ cycloalkyl group, X² is selected from the group consisting of —O—,—S—, —C(CF₃)₂—, —C(CH₃)₂—, —CH₂—, —SO₂—, and —NHCO—, Z is selected fromthe group consisting of H and C₁-C₈ linear, branched or cyclic alkyl andp is an integer from 1 to
 6. 5. A positive photosensitive resincomposition according to claim 1, wherein Ar² is a moiety derived from areactant selected from the group consisting of5(6)-diamino-1-(4-aminophenyl)-1,3,3-trimethylindane (DAPI),m-phenylenediamine, p-phenylenediamine,2,2′-bis(trifluoromethyl)-4,4′-diamino-1,1′-biphenyl,3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether,2,4-tolylenediamine, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenylmethane,3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ketone,3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 1,3-bis(4-aminophenoxy) benzene, 1,3-bis(3-amino-phenoxy) benzene, 1,4-bis(γ-aminopropyl)tetramethyldisiloxane,2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine,p-xylylenediamine, methylenediamine, tetramethylenediamine,pentamethylenediamine, hexamethylenediamine,2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine,heptamethylenediamine, 2,5-dimethylheptamethylenediamine,3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,octamethylenediamine, nonamethylenediamine,2,5-dimethylnonamethylenediamine, decamethylenediamine, ethylenediamine,propylenediamine, 2,2-dimethylpropylenediamine,1,10-diamino-1,10-dimethyldecane, 2,11-diaminidodecane, 1,12-diaminooctadecane, 2,17-diaminoeicosane,3,3′-dimethyl4,4′-diaminodiphenylmethane, bis(4-aminocyclohexyl)methane,3,3′-diaminodiphenylethane, 4,4′-diaminodiphenylethane,4,4′-diaminodiphenyl sulfide, 2,6-diaminopyridine, 2,5-diaminopyridine,2,6-diamino-4-trifluoromethylpyridine, 2,5-diamino-1,3,4,-oxadiazole,1,4-diaminocyclohexane, 4,4′-methylenedianiline,4,4′-methylene-bis(o-choloroaniline),4,4′-methylene-bis(3-methylaniline), 4,4′-methylene-bis(2-ethylaniline),4,4′-methylene-bis(2-methoxyaniline), 4,4′-oxy-dianiline,4,4′-oxy-bis-(2-methoxyaniline), 4,4′-oxy-bis-(2-chloroaniline),4,4′-thio-dianiline, 4,4′-thio-bis-(2-methylaniline),4,4′-thio-bis-(2-methyoxyaniline), and 4,4′-thio-bis-(2-chloroaniline).6. A positive photosensitive resin composition according to claim 1,wherein Ar³ is a moiety selected from the group consisting of

wherein X² is selected from the group consisting of —O—, —S—, C(CH₃)₂—,—C(CF₃)₂—, —CH₂—, —SO₂—, and —NHCO—.
 7. A positive photosensitive resincomposition according to claim 1, wherein Ar³ is a moiety derived from areactant selected from the group consisting of4,4′-diphenyletherdicarboxylic acid, terephthalic acid, isophthalicacid, isophthaloyl dichloride, phthaloyl dichloride, terephthaloyldichloride, 4,4′-diphenyletherdicarboxylic acid dichloride,dimethylisophthalate, dimethylphthalate, dimethylterphthalate,diethylisophthalate, diethylphthalate, diethylterphthalate and mixturesthereof.
 8. A positive photosensitive resin composition according toclaim 1, wherein G is selected from the group consisting of moieties ofthe following structures;


9. A positive photosensitive resin composition according to claim 1,wherein x is from about 10 to about 100 and y is from about 0 to 100.10. A positive photosensitive resin composition according to claim 1,wherein the diazoquinone photoactive compound (b) is selected from thegroup consisting of compounds of the formula:

wherein at least one Q is the moiety (IX) and another Q is the moiety(X) with any remainder being H and wherein moieties (IX) and (X) are.


11. A positive photosensitive resin composition according to claim 10,wherein the ratio of (IX) to (X) is from about 20/80 to 80/20 and Q=H isfrom about 2% to about 34%.
 12. A positive photosensitive resincomposition according to claim 1 additionally comprising an adhesionpromoter.
 13. A positive photosensitive resin composition according toclaim 12 wherein the adhesion promoter is one of the formula ofStructure (XI)

wherein each R¹⁰ is independently selected from the group consisting ofa C₁-C₄ alkyl group and a C₅-C₇ cycloalkyl group and each R¹¹ isindependently selected from the group consisting of a C₁-C₄ alkyl group,a C₁-C₄ alkoxy group, a C₅-C₇ cycloalkyl group and a C₅-C₇ cycloalkoxygroup; d is an integer from 0 to 3 and n is an integer from 1 to about6, and R¹² is a moiety selected from the group consisting of thefollowing moieties:

wherein each R¹³ and R¹⁴ are independently selected from the groupconsisting of a C₁C₄ alkyl group and a C5-C₇ cycloalkyl group, and R¹⁵is selected from the group consisting of a C₁-C₄ alkyl group and a C₅-C₇cycloalkyl group.
 14. A positive photosensitive resin compositionaccording to claim 1, wherein Ar¹ is a moiety derived from a reactantselected from the group consisting of2,2-bis(3-amino4-hydroxyphenyl)-hexafluoropropane,3,3′-dihydroxy-4,4′-diaminodiphenylether, 3,3′-dihydroxybenzidine,4,6-diaminoresorcinol, and 2,2-bis (3-amino4-hydroxyphenyl)propane andmixtures thereof, Ar³ is a moiety derived from a reactant selected fromthe group consisting of 4,4′-diphenyletherdicarboxylic acid,terephthalic acid, isophthalic acid, isophthaloyl dichloride, phthaloyldichloride, terephthaloyl dichloride, 4,4′-diphenyletherdicarboxylicacid dichloride, dimethylisophthalate, dimethylphthalate,dimethylterphthalate, diethylisophthalate, diethylphthalate,diethylterphthalate and mixtures thereof, the diazoquinone photoactivecompound (b) is selected from the group consisting of compounds of theformula:

wherein at least one Q is the moiety (IX) and another Q is the moiety(X) with any and wherein moieties (IX) and (X) are.

the composition additionally comprises and adhesion promoter wherein theadhesion promoter is one of the formula of Structure (XI)

wherein each R¹⁰ is independently selected from the group consisting ofa C₁-C₄ alkyl group and a C₅-C₇ cycloalkyl group and each R¹¹ isindependently selected from the group consisting of a C₁-C₄ alkyl group,a C₁-C₄ alkoxy group, a C₅-C₇ cycloalkyl group and a C₅-C₇ cycloalkoxygroup; d is an integer from 0 to 3 and n is an integer from 1 to about6, and R¹² is a moiety selected from the group consisting of thefollowing moieties:

wherein each R¹³ and R¹⁴ are independently selected from the groupconsisting of a C₁-C₄ alkyl group and a C₅-C₇ cycloalkyl group, and R¹⁵is selected from the group consisting of a C₁-C₄ alkyl group and a C₅-C₇cycloalkyl group.
 15. A process for forming a relief pattern on asubstrate, the process comprises the steps of: (a) coating on a suitablesubstrate, a positive-working photosensitive composition of claim 1,thereby forming a coated substrate; (b) prebaking the coated substrate;(c) exposing the prebaked coated substrate to actinic radiation; (d)developing the exposed coated substrate with an aqueous developer,thereby forming an uncured relief image on the coated substrate; and (e)baking the developed coated substrate at an elevated temperature,thereby curing the relief image.
 16. A process for forming a reliefpattern on a substrate, the process comprises the steps of: (a) coatingon a suitable substrate, a positive-working photosensitive compositionof claim 2 thereby forming a coated substrate; (b) prebaking the coatedsubstrate; (c) exposing the prebaked coated substrate to actinicradiation; (d) developing the exposed coated substrate with an aqueousdeveloper, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 17. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 3 thereby forming a coated substrate; (b) prebakingthe coated substrate; (c) exposing the prebaked coated substrate toactinic radiation; (d) developing the exposed coated substrate with anaqueous developer, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 18. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 4 thereby forming a coated substrate; (b) prebakingthe coated substrate; (c) exposing the prebaked coated substrate toactinic radiation; (d) developing the exposed coated substrate with anaqueous developer, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 19. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 5 thereby forming a coated substrate; (b) prebakingthe coated substrate; (c) exposing the prebaked coated substrate toactinic radiation; (d) developing the exposed coated substrate with anaqueous developer, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 20. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 6 thereby forming a coated substrate; (b) prebakingthe coated substrate; (c) exposing the prebaked coated substrate toactinic radiation; (d) developing the exposed coated substrate with anaqueous developer, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 21. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 7 thereby forming a coated substrate; (b) prebakingthe coated substrate; (c) exposing the prebaked coated substrate toactinic radiation; (d) developing the exposed coated substrate with anaqueous developer, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 22. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 8 thereby forming a coated substrate; (b) prebakingthe coated substrate; (c) exposing the prebaked coated substrate toactinic radiation; (d) developing the exposed coated substrate with anaqueous developer, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 23. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 9 thereby forming a coated substrate; (b) prebakingthe coated substrate; (c) exposing the prebaked coated substrate toactinic radiation; (d) developing the exposed coated substrate with anaqueous developer, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 24. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 10 thereby forming a coated substrate; (b)prebaking the coated substrate; (c) exposing the prebaked coatedsubstrate to actinic radiation; (d) developing the exposed coatedsubstrate with an aqueous developer, thereby forming an uncured reliefimage on the coated substrate; and (e) baking the developed coatedsubstrate at an elevated temperature, thereby curing the relief image.25. A process for forming a relief pattern on a substrate, the processcomprises the steps of: (a) coating on a suitable substrate, apositive-working photosensitive composition of claim 11 thereby forminga coated substrate; (b) prebaking the coated substrate; (c) exposing theprebaked coated substrate to actinic radiation; (d) developing theexposed coated substrate with an aqueous developer, thereby forming anuncured relief image on the coated substrate; and (e) baking thedeveloped coated substrate at an elevated temperature, thereby curingthe relief image.
 26. A process for forming a relief pattern on asubstrate, the process comprises the steps of: (a) coating on a suitablesubstrate, a positive-working photosensitive composition of claim 12thereby forming a coated substrate; (b) prebaking the coated substrate;(c) exposing the prebaked coated substrate to actinic radiation; (d)developing the exposed coated substrate with an aqueous developer,thereby forming an uncured relief image on the coated substrate; and (e)baking the developed coated substrate at an elevated temperature,thereby curing the relief image.
 27. A process for forming a reliefpattern on a substrate, the process comprises the steps of: (a) coatingon a suitable substrate, a positive-working photosensitive compositionof claim 13 thereby forming a coated substrate; (b) prebaking the coatedsubstrate; (c) exposing the prebaked coated substrate to actinicradiation; (d) developing the exposed coated substrate with an aqueousdeveloper, thereby forming an uncured relief image on the coatedsubstrate; and (e) baking the developed coated substrate at an elevatedtemperature, thereby curing the relief image.
 28. A process for forminga relief pattern on a substrate, the process comprises the steps of: (a)coating on a suitable substrate, a positive-working photosensitivecomposition of claim 14 thereby forming a coated substrate; (b)prebaking the coated substrate; (c) exposing the prebaked coatedsubstrate to actinic radiation; (d) developing the exposed coatedsubstrate with an aqueous developer, thereby forming an uncured reliefimage on the coated substrate; and (e) baking the developed coatedsubstrate at an elevated temperature, thereby curing the relief image.29. A substrate with a relief pattern formed by the process of claim
 1530. A substrate with a relief pattern formed by the process of claim 16.31. A substrate with a relief pattern formed by the process of claim 17.32. A substrate with a relief pattern formed by the process of claim 18.33. A substrate with a relief pattern formed by the process of claim 19.34. A substrate with a relief pattern formed by the process of claim 20.35. A substrate with a relief pattern formed by the process of claim 21.36. A substrate with a relief pattern formed by the process of claim 22.37. A substrate with a relief pattern formed by the process of claim 23.38. A substrate with a relief pattern formed by the process of claim 24.39. A substrate with a relief pattern formed by the process of claim 25.40. A substrate with a relief pattern formed by the process of claim 26.41. A substrate with a relief pattern formed by the process of claim 27.42. A substrate with a relief pattern formed by the process of claim 28.43. An article of commerce having incorporated therein a patterned imageof claim
 29. 44. An article of commerce having incorporated therein apatterned image of claim
 41. 45. An article of commerce of claim 43wherein the item of commerce is selected from the group consisting ofmemory devices, logic devices and plating stencils.
 46. An article ofcommerce of claim 44 wherein the item of commerce is selected from thegroup consisting of memory devices, logic devices and plating stencils.